CN104610178A - Preparation method of iodine atom-substituted bis-fluorophenyl heterocyclic conjugated monomer - Google Patents
Preparation method of iodine atom-substituted bis-fluorophenyl heterocyclic conjugated monomer Download PDFInfo
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- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
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- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
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- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
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- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
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Abstract
The invention relates to a preparation method of an iodine atom-substituted bis-fluorophenyl heterocyclic conjugated monomer. The preparation method comprises the following steps: firstly enabling a chemical compound with a bis-fluorophenyl heterocyclic conjugated structure to be reacted with lithium diisopropylamide, then adding an iodine elementary substance into a reaction system and finally introducing iodine atoms onto a benzene ring of the bis-fluorophenyl heterocyclic conjugated monomer. According to the method, the use of fuming sulfuric acid and other hazardous reagents is avoided, the synthetic efficiency and the experimental operation safety are improved, the yield is much higher than that obtained by a traditional iodization method, and the scale preparation and production are facilitated.
Description
Technical field
The invention belongs to Fine Organic Chemical technical field, be specially the preparation method that a kind of atomic iodine replaces two fluorine benzheterocycle conjugative monomer.
Background technology
Along with the development in epoch, the demand of the mankind to the energy is increasing, but the traditional resource such as oil, coal finally can be exhausted, and this just allows people feel all the more urgent to the development and utilization of new forms of energy.And sun power becomes the object of numerous scientist's research and utilization due to its general, harmless, permanent advantage always, wherein the solar cell of sun power is utilized to become one of research emphasis in photoelectric conversion mode.Silica-based solar cell is that developing the most permanent is also proven technique, at present commercialization the most, and the Laboratory efficiencies of monocrystalline silicon battery reaches 25.0%.But the sky high cost of silica-based solar cell, highly energy-consuming, production pollute the fatal defects such as large and result in it and can not realize for a long time applying widely.So, there are advantage [Materials Today, 17 (2014) 11-15 such as low cost, big area, flexibility, frivolous, solution processable; The Journal of Physical Chemistry Letters, 2 (2011) 3102-3113] polymer solar cells become the new primary study object of scientists.Over more than 20 year, researchist is by a large amount of organic donor of synthesis and acceptor material and continuing to optimize battery device, the Laboratory efficiencies of current single polymer layer organic photovoltaic cell has reached 10.36% [NatureCommunnications, 5 (2014) 5293], application prospect that is wide and light is had.
In numerous photoelectric material, containing diazosulfide, the photoelectric material of benzotriazole unit is widely used in the materials such as organic electroluminescent, organic photovoltaic cell and organic field effect tube.Compare with benzotriazole with diazosulfide, if the hydrogen on 5 and 6 carbon atoms on its phenyl ring is substituted by fluorine atom mainly contain following 3 advantages: (1) reduces the highest occupied molecular orbital(HOMO) energy level (HOMO) of polymkeric substance and lowest unocccupied molecular orbital energy level (LUMO) simultaneously, and having a little of optical band gap is a bit increased; (2) ionization energy of the polymkeric substance of fluoro is reduced, and is being improved with the charge transfer effciency in fullerene derivate PCBM Blending Processes; (3) fluorinated polymer all has smooth Conformation of the main chain in solution or film, make its accumulation under film more regular, its uptake factor is improved, especially at long wavelength region [the Journal of American Chemistry Society of absorption spectrum, 2012,134,14932-14944].
For a long time, two fluorine diazosulfide or benzotriazole introduce atomic iodine, usually need to use oleum and elemental iodine to react at 60 DEG C and generate [Angew.Chem.Int.Ed.2011,50,2995 – 2998].Oleum belongs to the control reagent of easily system poison, in use, if expose in atmosphere, and the sulphur trioxide (SO evaporated
3) form sulfuric acid droplets with the water vapour in air, potential safety hazard is caused to experiment operator.Preparation method of the present invention then first uses lithium diisopropylamine (LDA) with two fluorobenzene and on the phenyl ring of heterocyclic units, hydrogen atom reacts, and adds iodine subsequently, thus introduce atomic iodine in reaction system on the phenyl ring of two fluorine benzheterocycle.Compared with traditional method, the method has reaction process and easily makes malicious hazardous agents without the need to using oleum etc., and experimental implementation is safe and reliable, and substantially increases the advantages such as synthesis yield, can be used for the mass-producing preparation of iodinated monomer.
Summary of the invention
The object of the invention is to the deficiency overcoming prior art existence, provide the reliable atomic iodine of a kind of operational safety to replace the synthetic method of two fluorine benzheterocycle conjugative monomer.This atomic iodine replaces two fluorine benzheterocycle conjugative monomer can carry out coupling (or polymerization) by metal catalyzed coupling reaction with the aromatic ring group of other conjugation, and formation is to the small molecules of-receptor structure or donor-acceptor-donor structure or polymkeric substance.
Object of the present invention is achieved through the following technical solutions.
The preparation method of two fluorine benzheterocycle conjugative monomers that a kind of atomic iodine replaces, it comprises the following steps: the atomic reaction of hydrogen of lithium diisopropylamine (LDA) first with two fluorobenzene and on heterocyclic units (1) phenyl ring, iodine is added subsequently in reaction system, thus on two fluorine benzheterocycle conjugate unit phenyl ring, introduce atomic iodine, i.e. product (2 or 3); Reaction formula is
Wherein, Ar group is the conjugated structure of aromaticity, has following structural formula:
R is hydrogen, the alkyl of a 1-30 carbonatoms or wherein one or more carbon atoms are replaced by Sauerstoffatom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, nitro, phenyl, thienyl, or hydrogen atom is replaced by halogen atom.
Specifically implement ground further, the preparation method of two fluorine benzheterocycle conjugative monomers that described atomic iodine replaces comprises:
Under the atmosphere of inert gases of anhydrous, anaerobic, Diisopropylamine is dissolved in anhydrous organic solvent, and temperature Jiang Di Zhi – 78 DEG C, is slowly added dropwise to n-Butyl Lithium wherein, and stirring reaction generates lithium diisopropylamine (LDA); The two fluorine benzheterocycle conjugate unit of reactant is dissolved in anhydrous organic solvent, is added dropwise in LDA, and the equivalence ratio of the two fluorine benzheterocycle conjugate unit of reactant and LDA is determined by target product; After stirring reaction, will be dissolved in the iodine of anhydrous organic solvent, and to be disposablely added dropwise to, the equivalence ratio of iodine is determined by target product; After iodine solution dropwises, naturally rise to room temperature, stirring reaction spends the night; Target product is two fluorine benzheterocycle conjugative monomers that diiodo-replaces, then two fluorine Benzoheterocyclic compounds: lithium diisopropylamine: the equivalent proportioning of elemental iodine should be 1:2:2.3; If target product is two fluorine benzheterocycle conjugative monomers that single iodine replaces, then two fluorine Benzoheterocyclic compounds: lithium diisopropylamine: the equivalent proportioning of elemental iodine should be 1:1:1.15.
Described organic solvent is tetrahydrofuran (THF), ether, normal hexane, methylene dichloride, chloroform, the one in toluene.
Compared with existing technology, the invention has the advantages that:
Reaction process is without the need to using easily poison processed, the hazardous agents such as oleum, and experimental implementation is safe and reliable, and substantially increases synthesis yield, is conducive to mass-producing preparation and produces.
Embodiment
Be described further enforcement of the present invention below in conjunction with example, but enforcement of the present invention and protection being not limited thereto, if there is not specified part below, is all that those skilled in the art can refer to existing techniques in realizing.
The atomic iodine of following instance replaces shown in the following reaction formula of syntheti c route of two fluorine benzheterocycle conjugative monomer: two fluorine benzheterocycle (Ar) compounds 1 synthesized by methodology of organic synthesis are reacted with lithium diisopropylamine (LDA) under low-temperature anhydrous condition, then in reaction system, elemental iodine is added, finally on two fluorine benzheterocycle, introduce atomic iodine, i.e. diiodo-substituted monomer (2) or single iodine substituted monomer (3).
(1) preparation of lithium diisopropylamine (LDA): under nitrogen atmosphere, the tetrahydrofuran solution of 0.1g/mL Diisopropylamine (1.1 equivalent) is cooled to-78 DEG C, slowly drip the n-Butyl Lithium (2.5mol/L hexane solution) of 1 equivalent to solution, after dropwising, remain on-78 DEG C of reactions 1 hour.
(2) iodination reaction: the solution substrate (two fluorine benzheterocycle conjugated compound) of 1.0 equivalents and anhydrous organic solvent being made into 0.1g/L, is then added drop-wise in LDA gradually, reacts 1 hour at-78 DEG C; The elemental iodine of 2.3 equivalents (preparing diiodo-substituted monomer 2) or 1.15 equivalents (preparing single iodine substituted monomer 3) and anhydrous organic solvent are made into the solution of 0.06g/L, and by its direct dropwise reaction system, system rises to room temperature naturally, and stirring is spent the night.
(3) aftertreatment: reaction solution is poured in the aqueous solution of sodium bisulfite and stir, elemental iodine is removed, and with methylene dichloride, the solvent to product favorable solubility such as trichloromethane extracts, and gets organic layer, and washs with saturated sodium-chloride water solution, anhydrous magnesium sulfate drying, filter, solvent removes by underpressure distillation, and the crude product obtained is purified by recrystallization or column chromatography.
By concrete example, the invention will be further described more below.
Embodiment 1
The preparation of the iodo-2-dodecyl of 4,7-bis--5,6 two fluoro-2H-benzo [d] [1,2,3] triazole
Synthetic route is as follows:
In 250mL long-neck there-necked flask, under argon atmospher, add Diisopropylamine (1.73g, 17.03mmol, 2.2 equivalents) and 30mL tetrahydrofuran (THF), be cooled to-78 DEG C, drip n-Butyl Lithium (15.48mmol, 6.2mL, 2.5mol/L, equivalent), complete, react 1 hour, then by 2-dodecyl-5, 6 two fluoro-2H-benzos [d] [1, 2, 3] triazole (2.5g, 7.74mmol, 1 equivalent) with the tetrahydrofuran (THF) wiring solution-forming of 25mL, drip gradually to reaction solution gradually, complete, react 40 minutes, drip the tetrahydrofuran solution (4.52g of iodine more wherein, 17.8mmol, 2.3 equivalent, 75mL tetrahydrofuran (THF)), complete, stir after 15 minutes, be placed in room temperature, stirring is spent the night.Aftertreatment: add S-WAT and stir removing iodine, be then poured into water, dichloromethane extraction, saturated sodium-chloride water solution is washed, anhydrous magnesium sulfate drying.Cross post with sherwood oil and methylene dichloride mixed solvent, obtain the product of oily liquids, be long placed in as solid, 3.7g (productive rate: 84%).Proton nmr spectra: (CDCl
3) δ (ppm) 4.75 – 4.71 (m, 2H), 2.17 – 2.06 (m, 2H), 1.42 – 1.18 (m, 18H), 0.87 (t, 3H). carbon-13 nmr spectra: (CDCl
3) δ (ppm) 152.44,152.30,150.76,150.62,140.79,140.77,140.75,122.36,122.29,121.11,120.90,57.47,31.95,30.17,29.65,29.63,29.52,29.39,29.37,29.00,26.51,22.73,14.16. mass spectrum: calculated value: 575.01; Measured value: 576.0.
Embodiment 2
The preparation of 4,7-bis-iodo-5,6 difluoro benzo [d] [1,2,5] thiadiazoles
In 250mL long-neck there-necked flask, under argon atmospher, add Diisopropylamine (3.9g, 15.3mmol, 2.2 equivalents) and 30mL tetrahydrofuran (THF), be cooled to-78 DEG C, drip n-Butyl Lithium (34.8mmol, 14.0mL, 2.5mol/L, 2 equivalents), complete, react 1 hour, then by 5, 6 difluoro benzos [d] [1, 2, 5] thiadiazoles (3g, 17.4mmol, 1 equivalent) with the tetrahydrofuran (THF) wiring solution-forming of 30mL, drip gradually to reaction solution gradually, complete, react 40 minutes, drip the tetrahydrofuran solution (10.16g of iodine more wherein, 40.02mmol, 2.3 equivalent, 170mL tetrahydrofuran (THF)), complete, stir after 15 minutes, be placed in room temperature, stirring is spent the night.Aftertreatment: add S-WAT and stir removing iodine, be then poured into water, dichloromethane extraction, saturated sodium-chloride water solution is washed, anhydrous magnesium sulfate drying.Underpressure distillation goes out desolventizing, and the solid ethanol obtained and the mixed solvent recrystallization of toluene, obtain faint yellow solid 6.5g (productive rate: 88%).Mass spectrum: calculated value: 423.78; Measured value: 424.60. ultimate analysis: calculated value: C, 17.00%; N, 6.61%; S, 7.56%; Measured value: C, 16.82%; N, 6.22%; S, 7.13%.
Embodiment 3
5,8-bis-iodo-6, the preparation of 7 two fluoro-2,3-two (4-(octyloxy) phenyl) quinoxalines
In 100mL long-neck there-necked flask, under argon atmospher, add Diisopropylamine (0.78g, 7.66mmol, 2.2 equivalents) and 10mL tetrahydrofuran (THF), be cooled to-78 DEG C, drip n-Butyl Lithium (6.96mmol, 2.8mL, 2.5mol/L, 2 equivalents), complete, react 1 hour, then by 6, 7 two fluoro-2, two (4-(octyloxy) phenyl) quinoxaline (2.0g of 3-, 3.48mmol, 1 equivalent) with the tetrahydrofuran (THF) wiring solution-forming of 20mL, drip gradually to reaction solution gradually, complete, react 40 minutes, drip the tetrahydrofuran solution (2.04g of iodine more wherein, 8.00mmol, 2.3 equivalent, 35mL tetrahydrofuran (THF)), complete, stir after 15 minutes, be placed in room temperature, stirring is spent the night.Aftertreatment: add S-WAT and stir removing iodine, be then poured into water, dichloromethane extraction, saturated sodium-chloride water solution is washed, anhydrous magnesium sulfate drying.Cross post with sherwood oil and methylene dichloride mixed solvent, obtain 2.3g solid (productive rate: 80%).Mass spectrum: calculated value: 826.13; Measured value: 827.04. ultimate analysis: calculated value: C, 52.31%; H, 5.12%; N, 3.39%; Measured value: C, 51.63%; H, 4.98%; N, 3.12%.
Embodiment 4
The preparation of fluoro-10,13-bis-iodo-2,7-dioctyl dibenzo [a, the c] azophenlyene of 11,12-bis-
In 250mL long-neck there-necked flask, under argon atmospher, add Diisopropylamine (0.66g, 6.51mmol, 2.2 equivalents) and 10mL tetrahydrofuran (THF), be cooled to-78 DEG C, drip n-Butyl Lithium (5.92mmol, 2.37mL, 2.5mol/L, 2 equivalents), complete, react 1 hour, then by 11, 12-bis-fluoro-2, 7-dioctyl dibenzo [a, c] azophenlyene (1.6g, 2.96mmol, 1 equivalent) and 25mL tetrahydrofuran (THF) wiring solution-forming, drip gradually to reaction solution gradually, complete, react 40 minutes, drip the tetrahydrofuran solution (1.73g of iodine more wherein, 6.81mmol, 2.3 equivalent, 30mL tetrahydrofuran (THF)), stir after 15 minutes, be placed in room temperature, stirring is spent the night.Aftertreatment: add S-WAT and stir removing iodine, be then poured into water, dichloromethane extraction, saturated sodium-chloride water solution is washed, anhydrous magnesium sulfate drying.Post is crossed, 1.9g (productive rate: 82%) with sherwood oil and methylene dichloride mixed solvent.Mass spectrum: calculated value: 792.12; Measured value: 792.96. ultimate analysis: calculated value: C, 54.56%; H, 5.09%; N, 3.53%; Measured value:: C, 52.43%; H, 4.97%; N, 3.37%;
Embodiment 5
The preparation of 4,7-bis-iodo-5,6 difluoro benzo [d] [1,2,5] selenium diazole
In 250mL long-neck there-necked flask, under argon atmospher, add Diisopropylamine (2.94g, 29.04mmol, 2.2 equivalents) and 30mL tetrahydrofuran (THF), be cooled to-78 DEG C, drip n-Butyl Lithium (26.4mmol, 10.6mL, 2.5mol/L, 2 equivalents), complete, react 1 hour, then by 5, 6 difluoro benzos [d] [1, 2, 5] selenium diazole (2.9g, 13.2mmol, 1 equivalent) with the tetrahydrofuran (THF) wiring solution-forming of 30mL, drip gradually to reaction solution gradually, complete, react 40 minutes, drip the tetrahydrofuran solution (7.7g of iodine more wherein, 30.3mmol, 2.3 equivalent, 130mL tetrahydrofuran (THF)), complete, stir after 15 minutes, be placed in room temperature, stirring is spent the night.Aftertreatment: add S-WAT and stir removing iodine, be then poured into water, dichloromethane extraction, saturated sodium-chloride water solution is washed, anhydrous magnesium sulfate drying.Underpressure distillation goes out desolventizing, the solid with ethyl acetate recrystallization obtained, and obtains yellow solid 5.1g (productive rate: 82%).Mass spectrum: calculated value: 471.73; Measured value: 472.62. ultimate analysis: calculated value: C, 15.31; N, 5.95; Measured value: C, 15.17%; N, 5.62%.
Embodiment 6
The preparation of iodo-6,7-bis-fluoro-2, the 3-dimethyl-quinoxalines of 5,8-bis-
In 250mL long-neck there-necked flask, under argon atmospher, add Diisopropylamine (1.39g, 13.64mmol, 2.2 equivalents) and 15mL tetrahydrofuran (THF), be cooled to-78 DEG C, drip n-Butyl Lithium (12.4mmol, 5mL, 2.5mol/L, 2 equivalents), complete, react 1 hour, then by 6, 7-bis-fluoro-2, 3-dimethyl-quinoxaline (1.2g, 6.2mmol, 1 equivalent) with the tetrahydrofuran (THF) wiring solution-forming of 15mL, drip gradually to reaction solution gradually, complete, react 40 minutes, drip the tetrahydrofuran solution (3.6g of iodine more wherein, 14.3mmol, 2.3 equivalent, 60mL tetrahydrofuran (THF)), complete, stir after 15 minutes, be placed in room temperature, stirring is spent the night.Aftertreatment: add S-WAT and stir removing iodine, be then poured into water, dichloromethane extraction, saturated sodium-chloride water solution is washed, anhydrous magnesium sulfate drying.Underpressure distillation goes out desolventizing, and the solid ethanol obtained and the mixed solvent recrystallization of toluene, obtain faint yellow solid 2.3g (productive rate: 76%).Mass spectrum: calculated value: 445.86; Measured value: 446.90. ultimate analysis: calculated value: C, 26.93%; H, 1.36%; N, 6.28%; Measured value: C, 26.77%; H, 1.22%; N, 6.09%.
Embodiment 7
The preparation of the iodo-2-dodecyl of 4--5,6 two fluoro-2H-benzo [d] [1,2,3] triazole
In 250mL long-neck there-necked flask, under argon atmospher, add Diisopropylamine (0.7g, 6.82mmol.1.1 equivalent) and 15mL tetrahydrofuran (THF), be cooled to-78 DEG C, drip n-Butyl Lithium (6.2mmol, 2.5mL, 2.5mol/L, 1 equivalent), complete, react 1 hour, then by 2-dodecyl-5, 6 two fluoro-2H-benzos [d] [1, 2, 3] triazole (2g, 6.2mmol, 1 equivalent) with the tetrahydrofuran (THF) wiring solution-forming of 15mL, drip gradually to reaction solution gradually, complete, react 40 minutes, drip the tetrahydrofuran solution (1.8g of iodine more wherein, 7.12mmol, 1.15 equivalent, 30mL tetrahydrofuran (THF)), complete, stir after 15 minutes, be placed in room temperature, stirring is spent the night.Aftertreatment: add S-WAT and stir removing iodine, be then poured into water, dichloromethane extraction, saturated sodium-chloride water solution is washed, anhydrous magnesium sulfate drying.Cross post with sherwood oil and methylene dichloride mixed solvent, obtain the compound of oily liquids, 2.3g (productive rate: 83%).Mass spectrum: calculated value: 449.11; Measured value: 449.97. ultimate analysis: calculated value: C, 48.12%; H, 5.83%; N, 9.35%; Measured value: C, 47.97%; H, 5.68%; N, 9.22%.
Embodiment 8
The preparation of 4-iodo-5,6 difluoro benzo [d] [1,2,5] thiadiazoles
In 100mL long-neck there-necked flask, under argon atmospher, add Diisopropylamine (0.65g, 6.38mmol, 1.1 equivalents) and 10mL tetrahydrofuran (THF), be cooled to-78 DEG C, drip n-Butyl Lithium (5.8mmol, 2.4mL, 2.5mol/L, 1 equivalent), complete, react 1 hour, then by 5, 6 difluoro benzos [d] [1, 2, 5] thiadiazoles (1g, 5.8mmol, 1 equivalent) with the tetrahydrofuran (THF) wiring solution-forming of 10mL, drip gradually to reaction solution gradually, complete, react 40 minutes, drip the tetrahydrofuran solution (1.7g of iodine more wherein, 6.7mmol, 1.15 equivalent, 30mL tetrahydrofuran (THF)), complete, stir after 15 minutes, be placed in room temperature, stirring is spent the night.Aftertreatment: add S-WAT and stir removing iodine, be then poured into water, dichloromethane extraction, saturated sodium-chloride water solution is washed, anhydrous magnesium sulfate drying.Underpressure distillation goes out desolventizing, and the solid ethanol obtained and the mixed solvent recrystallization of toluene, obtain solid 1.4g (productive rate: 80%).Mass spectrum: calculated value: 297.89; Measured value: 298.67. ultimate analysis: calculated value: C, 24.18%; H, 0.34%; N, 9.40%; S, 10.76%; Measured value: C, 23.92%; H, 0.26%; N, 9.14%; S, 10.48%.
Claims (3)
1. the preparation method of two fluorine benzheterocycle conjugative monomers of an atomic iodine replacement, it is characterized in that comprising the following steps: the atomic reaction of hydrogen of lithium diisopropylamine (LDA) first with two fluorobenzene and on heterocyclic units (1) phenyl ring, iodine is added subsequently in reaction system, thus on two fluorine benzheterocycle conjugate unit phenyl ring, introduce atomic iodine, i.e. product (2 or 3); Reaction formula is
Wherein, Ar group is the conjugated structure of aromaticity, has one of following structural formula:
R be hydrogen, the alkyl of a 1-30 carbonatoms or wherein one or more carbon atoms by Sauerstoffatom, thiazolinyl,
Alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, nitro, phenyl, thienyl replace, or hydrogen is former
Son is replaced by halogen atom.
2. the preparation method of two fluorine benzheterocycle conjugative monomers of atomic iodine replacement according to claim 1, is characterized in that specifically comprising:
Under the atmosphere of inert gases of anhydrous, anaerobic, Diisopropylamine is dissolved in anhydrous organic solvent, and temperature Jiang Di Zhi – 78 DEG C, is slowly added dropwise to n-Butyl Lithium wherein, and stirring reaction generates lithium diisopropylamine (LDA); The two fluorine benzheterocycle conjugate unit of reactant is dissolved in anhydrous organic solvent, is added dropwise in LDA, and the equivalence ratio of the two fluorine benzheterocycle conjugate unit of reactant and LDA is determined by target product; After stirring reaction, will be dissolved in the iodine of anhydrous organic solvent, and to be disposablely added dropwise to, the equivalence ratio of iodine is determined by target product; After iodine solution dropwises, naturally rise to room temperature, stirring reaction spends the night; Target product is two fluorine benzheterocycle conjugative monomers that diiodo-replaces, then two fluorine Benzoheterocyclic compounds: lithium diisopropylamine: the equivalent proportioning of elemental iodine should be 1:2:2.3; If target product is two fluorine benzheterocycle conjugative monomers that single iodine replaces, then two fluorine Benzoheterocyclic compounds: lithium diisopropylamine: the equivalent proportioning of elemental iodine should be 1:1:1.15.
3. the preparation method of two fluorine benzheterocycle conjugative monomers of atomic iodine replacement according to claim 2, is characterized in that described organic solvent is tetrahydrofuran (THF), ether, normal hexane, methylene dichloride, chloroform, the one in toluene.
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| CN105777666A (en) * | 2016-03-27 | 2016-07-20 | 华南理工大学 | Preparation method of iodine atom-substituted methylic fluorobenzene and heterocyclic compound |
| WO2017174619A1 (en) * | 2016-04-08 | 2017-10-12 | Merck Patent Gmbh | Intermediates and procedures for the synthesis of functional materials |
| CN108264516A (en) * | 2016-12-30 | 2018-07-10 | 深圳市星源材质科技股份有限公司 | A kind of preparation method and application of the conjugated molecule based on fluoro diazosulfide |
| CN112321512A (en) * | 2020-11-25 | 2021-02-05 | 上海吉奉生物科技有限公司 | Synthesis method of 4, 5-diiodo-1H-imidazole |
| CN114560871A (en) * | 2021-04-19 | 2022-05-31 | 中国科学院大学 | Synthesis method of selective substituted functionalized dithienyl imide luminescent material |
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| CN105777666A (en) * | 2016-03-27 | 2016-07-20 | 华南理工大学 | Preparation method of iodine atom-substituted methylic fluorobenzene and heterocyclic compound |
| WO2017174619A1 (en) * | 2016-04-08 | 2017-10-12 | Merck Patent Gmbh | Intermediates and procedures for the synthesis of functional materials |
| CN108884390A (en) * | 2016-04-08 | 2018-11-23 | 默克专利股份有限公司 | For synthesizing the intermediate and process of functional material |
| US10711138B2 (en) | 2016-04-08 | 2020-07-14 | Merck Patent Gmbh | Intermediates and procedures for the synthesis of functional materials |
| CN108884390B (en) * | 2016-04-08 | 2022-05-31 | 默克专利股份有限公司 | Intermediates and procedures for the synthesis of functional materials |
| CN108264516A (en) * | 2016-12-30 | 2018-07-10 | 深圳市星源材质科技股份有限公司 | A kind of preparation method and application of the conjugated molecule based on fluoro diazosulfide |
| CN112321512A (en) * | 2020-11-25 | 2021-02-05 | 上海吉奉生物科技有限公司 | Synthesis method of 4, 5-diiodo-1H-imidazole |
| CN114560871A (en) * | 2021-04-19 | 2022-05-31 | 中国科学院大学 | Synthesis method of selective substituted functionalized dithienyl imide luminescent material |
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| CN104610178B (en) | 2018-01-05 |
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